Fiber Reinforced Flexible Foams

ABSTRACT

A flexible foam composition comprising a flexible foam structure comprising a plurality of struts, and a plurality of fibers, where a majority of the fibers are associated with the struts. The fibers may be thermally conductive fibers. The fibers include, but are not necessarily limited to, homopolymer and/or copolymer fibers having a glass transition temperature (Tg) of −50° C. (−58° F.) or greater, carbon fibers, animal-based fibers, plant-based fibers, metal fibers, and combinations thereof. The presence of fibers can impart to the flexible foam composition greater indentation force deflection (IFD), greater static thermal conductivity, improved compression set, improved height retention or durability, and/or a combination of these improvements. The flexible foam composition may be polyurethane foam, latex foam, polyether polyurethane foam, viscoelastic foam, high resilient foam, polyester polyurethane foam, foamed polyethylene, foamed polypropylene, expanded polystyrene, foamed silicone, melamine foam, among others.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication No. 62/588,749 filed Nov. 20, 2017, incorporated herein byreference in its entirety.

TECHNICAL FIELD

The invention relates to compositions for flexible foams in which thestruts within the foam are aligned with and/or associated with aplurality of fibers, and more particularly relates to flexible foamcompositions where in non-limiting embodiments the flexible foams arepolyurethane or latex foams and the fibers are carbon fibers, metalfibers, plant-based fibers, animal-based fibers, and/or syntheticfibers.

TECHNICAL BACKGROUND

Polyurethane foams are typically made from the reaction of one or morepolyols with one or more isocyanates in the presence of gelation andblowing catalysts and other additives. They are used in a wide varietyof industrial and household items ranging from interior components ofairplanes and automobiles to residential appliances, furniture, bedding,and bath items.

Because of the wide ranging use of polyurethane foams, it is importantfor the foams to be durable, strong, less susceptible to deformation anddegradation, and more thermally conductive.

Over the years, various additives and other materials have beenincorporated into the polyurethane foam making process to improve theirperformance for the end uses of the foams. In addition, polyurethane andother foams have been subjected to different types of surface treatmentto achieve the same, in a non-limiting embodiment having a substanceinfused into the surface of a flexible foam, such as a gel, water-basedcoatings, or solvent-based coatings.

Despite these efforts, there still remains a need to develop flexiblefoams, particularly polyurethane foams, latex foams, surface infusedfoams, coated foams, elastomer/gel foams, and the like having improvedproperties, such as greater indentation force deflection (IFD), greaterstatic thermal conductivity, improved compression set, and/or improvedheight retention or durability, for better performance in anyapplication use.

SUMMARY

There is provided, in a non-restrictive embodiment, a flexible foamcomposition comprising a polyurethane foam structure, where thepolyurethane foam structure comprises a plurality of struts and aplurality of fibers, where a majority of the fibers are associated withthe struts. Optionally the fibers are selected from the group consistingof carbon fibers, polymer fibers having a glass transition temperature(Tg) of −50° C. (−58° F.) or greater, homopolymer and/or copolymerfibers having a glass transition temperature (Tg) of or −50° C. (−58°F.) greater, plant-based fibers, animal-based fibers, metal fibers, andcombinations thereof.

There is also provided, in another non-limiting embodiment, a flexiblefoam structure (optionally a polyurethane foam structure made by aprocess comprising reacting one or more polyols and one or morepolyisocyanates in the presence of at least one gelation catalyst),where the flexible foam structure comprises a plurality of struts and aplurality of fibers, where a majority of the fibers are associated withthe struts and are substantially parallel to their respective associatedstrut; and where the fibers are selected from the group consisting ofcarbon fibers, homopolymer and/or copolymer fibers having a glasstransition temperature (Tg) of 50° C. (122° F.) or greater, polymerfibers having a glass transition temperature (Tg) of −50° C. (−58° F.)or greater, and combinations thereof. The fibers have a diameter betweenabout 0.1 to about 25 microns, a length between about 30 to about 490microns. In the case where the flexible foam is polyurethane foam, thefoam has a fiber loading based on the amount of polyol ranges from about0.01 to about 50 pph. In the case where the flexible foam is other thanpolyurethane foam, the fiber loading ranges from about 0.01 to 30percent by weight in the final flexible foam.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a microphotograph of a plurality of thermally conductivefiber-reinforced struts of in one non-limiting embodiment of apolyurethane foam composition discussed herein;

FIG. 2 is a microphotograph of a plurality of thermally conductivefiber-reinforced struts of in another non-limiting embodiment of apolyurethane foam composition discussed herein.

FIG. 3 is a graph illustrating the indentation force deflection (IFD)value of exemplary thermally conductive carbon-fiber reinforcedpolyurethane foams as described and discussed herein in relation to theamount of carbon fiber loaded into the polyol that is reacted to makethe polyurethane foam;

FIG. 4 is a bar graph illustrating that including flexible fiber reducesfatigue losses as measured by IFD for nickel fiber, copper fiber andchitosan fiber at two different usage levels, as described and discussedherein; and

FIG. 5 is a graph illustrating that flexible fiber reduces compressionlosses as measured by height loss for three different trials withdifferent fiber loadings into the polyol that is reacted to make thepolyurethane foam.

It will be appreciated that the various elements and details shown inphotographic and graphic illustrations are not necessarily to scale orproportion, and that many details have been removed or simplified forclarity. Furthermore, this disclosure is not necessarily limited to theembodiments or details depicted or discussed in the Figures.

DETAILED DESCRIPTION

It has been discovered that fiber-reinforced polyurethane foamcompositions that are made by loading an amount of fibers into the oneor more polyols that reacts with one or more polyisocyanates in thepresence of at least one gelation catalyst and other additives, such asgels including carbon fiber (CF) gels, results in a polyurethane foamthat may have a greater indentation force deflection (IFD) as comparedwith an otherwise identical polyurethane foam composition absent thecarbon fibers, may have a greater static thermal conductivity and/orimproved height retention or durability as compared with an otherwiseidentical polyurethane foam composition absent the carbon fibers, and/ormay have an improved compression set as compared with an otherwiseidentical polyurethane foam composition absent the carbon fibers. It hasalso been discovered that fibers may be included in a wide variety offlexible foam compositions to achieve one or more of these improvements.The methods and compositions herein do not relate to rigid foams. In onenon-limiting embodiment, the fibers are mixed into a one or more liquidcomponents of the reacting flexible foam formulation to make a pumpableslurry. In the case of flexible polyurethane foams, liquid componentsmay comprise of any liquid component such as polyol, isocyanate,silicone surfactant, etc. conventionally used in the manufacture ofpolyurethane foams. Alternatively, there may be considered using asolids funnel or venturi effect and mixer in a trough after the foamingchemicals have been introduced through the mixhead but before gelationof the flexible foam.

In a non-restrictive embodiment, flexible foam composition comprises aflexible foam structure, where the flexible foam structure includes aplurality of struts and a plurality of fibers, where a majority of thefibers are associated with the struts. By “a majority” is meant greaterthan 50%, although in a non-limiting embodiment at least 60% of thefibers are associated with the struts, alternatively at least 70% of thefibers are so associated. As defined herein, flexible foam “struts” arean elastomer portion of a flexible foam that exist to form the cells. Ina more specific non-limiting embodiment, struts are the elastomericmaterial between nodes. By “associated” is meant that a fiber is onand/or within the strut; that is, a fiber may be wholly within a strut,or may be only on the surface of the strut, or some combination of thesepositions. A fiber may protrude from a strut. Also within the structuresdefined herein are cases where a fiber, such as a reinforcing fiber,extends from one strut through a node and into another strut. In anothernon-limiting embodiment a majority of the fibers are substantiallyparallel to their respective associated strut. That is, if a strut isconsidered as linear or with a direction, the fiber is aligned with orsubstantially parallel thereto, in one non-limiting embodiment at leastwithin 35° of a strut axis; alternatively at least within 25° of a strutaxis; and in another non-restrictive embodiment at least within 15° of astrut axis. Various orientations of fibers on and within struts may bereadily seen in the microphotographs of polyurethane flexible foam inFIGS. 1 and 2 herein.

The fibers that may be used to align with struts of the polyurethanefoam structure and reinforce the polyurethane foam structure are, in anon-limiting embodiment, loaded into one or more polyols used to makethe polyurethane foam structure, where fiber loading based on the amountof polyol could range from about 0.01 pph independently to about 50 pph;in another non-restrictive version from about 0.1 independently to about30 pph; alternatively from about 0.25 independently to about 15 pph. Theunit “pph” for purposes of this disclosure is defined to mean parts perhundred parts of polyol and reflects a measure of weight of a fiber thatis added to every 100 of the same measure of weight of polyol used tomake the foam. When the term “independently” is used herein with respectto a range, any threshold may be used together with any other thresholdto give a suitable alternative range. For example in this case asuitable range is from about 0.01 pph to about 15 pph. In the case wherethe flexible foam is other than polyurethane foam, the fibers may bepresent in an amount of from about 0.01 independently to about 30 wt %of the final flexible foam; alternatively from about 0.5 independentlyto about 10 wt % of the final flexible foam. In a differentnon-restrictive version the fibers are thermally conductive fibers andthe thermally conductive fiber loading is an amount effective toincrease the static thermal conductivity as compared with an otherwiseidentical polyurethane foam composition absent the thermally conductivefibers. The amount of increase of static thermal conductivity may be atleast 10%; alternatively at least 25%; and in another non-limitingembodiment at least 50%. Thermally conductive fibers are defined in onenon-limiting embodiment as having a thermal conductivity of at least 1W/m-K, alternatively at least 5 W/m-K, in another non-limiting versionat least 20 W/m-K, alternatively at least about 100 W/m-K, or at least250 W/m-K, even at least 500 W/m-K. The thermal conductivity of carbonfiber in epoxy in plane (as opposed to in transverse) is at least about5-7 W/m-K. The thermal conductivity of carbon fiber is at least about21-180 W/m-K. The thermal conductivity of high modulus mesophase pitchcarbon fiber in the fiber direction is at least about 500 W/m-K. In adifferent non-limiting embodiment the fibers are non-thermallyconductive or not very conductive; examples of non-thermally conductivefibers include, but are not necessarily limited to, natural fibers suchas cotton, silk, and the like. As defined herein, carbon fibers do notinclude carbon nanotubes, do not include carbon black, and/or do notinclude activated carbon.

The fibers may be carbon fibers, and/or may be polymer fibers that havea glass transition temperature (Tg) of −50° C. (−58° F.) or greater;alternatively of 310K (99° F.) or greater; in another non-limitingembodiment a Tg of 323K (50° C. or 122° F.) or higher.

The polymer fibers may be and include homopolymers or co-polymers.Homopolymer and/or copolymer fibers suitable herein may have a glasstransition temperature (Tg) of about 50° C. (122° F.) or greater.Suitable polymer fibers include, but are not limited to, fibers madefrom the polymers listed in Table 1 below.

In a non-restrictive embodiment, the fibers may have a diameter betweenabout 0.1 microns independently to about 25 microns; in anothernon-restrictive version from about 2 microns independently to about 20microns; alternatively from about 4 independently to about 12 microns;in a different non-limiting embodiment from about 1 micron independentlyto about 15 microns. The fibers may have a length in one non-limitingembodiment of between about 30 microns independently to about 490microns; in another non-restrictive version between about 40 micronsindependently to about 390 microns; alternatively from about 50 to about180 microns; in another non-restrictive version from about 90 to about160 microns, and in still another non-limiting embodiment from about 75to about 90 microns. In another non-restrictive embodiment, the fiberlength is less than the average foam cell diameter. The average foamcell diameter may range from about 100 independently to about 3500microns; alternatively from about 250 independently to about 1000microns.

TABLE 1 Amorphous Polymers with Tg of 310° K (99° F.) or Greater PolymerName Tg (K) Poly(p-phenylene terephthalamide), e.g. KEVLAR ®, PPTA 600Poly(p-phenylene), PPP 538 Poly(m-phenylene terephthalamide), e.g.NOMEX ® MPDI 537 Poly(bisphenol S-alt-terephthalic acid) 519Poly(methacrylic acid), PMAA 501 Poly(2,6,3′,5′-tetrachloro bisphenol Acarbonate) 500 Poly(2,6-diphenyl-p-phenylene oxide) 497 Poly(tetramethylbisphenol A terephthalate) 492 Poly(1,4-phenylene ether-sulfone), PES490 Poly(2,6-dimethyl-p-phenylene oxide), PPO 487 Poly(tetrachloroBisphenol A terephthalate) 483 Poly(1,4-biphenyl ether ether sulfone),PPSU 482 Poly(1,4-phenylene ether ether sulfone), PEE 479 Poly(bisphenolAP isophthalate) 473 Poly(tetramethyl Bisphenol A carbonate) 467Poly(Bisphenol AP carbonate) 460Poly{[bis(4-chlorophenyl)sulfone]-alt-[bisphenol-A]}, PSU 457Poly(Bisphenol C terephthalate) 445 Poly(α-methylstyrene), PaMS 445Poly(acrylamide) 438 Poly(ether ketone ketone), PEKK 437 Poly(methylcyanoacrylate) 436Poly{hydroquinone-alt-[1,4-bis(4-fluorobenzoyl)benzene]}, 433 PEEKKPoly(4-hydroxystyrene), PVAc, PVA 430 Poly(4,4′-dichlorobenzophenone),PEK 428 Poly(Bisphenol A carbonate) 424 Poly(4-phenylstyrene) 423Poly(ethyl cyanoacrylate) 422Poly[(hydroquinone)-alt-(4,4′-dichlorobenzophenone)], PEEK 420Poly(Bisphenol E carbonate) 416 Poly(Bisphenol B carbonate) 415Poly{(ethylene glycol)-alt-[bis(4-isocyanatophenyl)methane]}, 412 EG50 - MDI Poly(4-bromostyrene) 411 Poly(2-methylstyrene) 409Poly(diisopropyl Bisphenol A terephthalate) 408 Poly(4,4′-methylenedioxydibenzoic anhydride) 407 Poly(Bisphenol F carbonate) 407Poly(4-tert-butylcyclohexyl methacrylate) 403 Poly(4-tert-butylstyrene)402 Poly(1,4-cyclohexanecarbonate) 400 Poly(4-chlorostyrene) 398Poly(2-chlorostyrene) 395 Poly(cyclohexylethene) 393 Teflon, PTFE 392Poly(ethylene 2,6-naphthalate) 392 Poly(4,4′-thiodiphenylene carbonate)391 Poly(heptane-1,7-diyl terephthalamide) 390 Poly(cyclohexylmethacrylate) 389 Poly(tert-butyl methacrylate) 388Poly(methacrylonitrile) 388 Poly(4-methoxystyrene) 386 Poly(vinyl phenylsulfide) 386 Poly(isophthalic anhydride) 385 Poly(Bisphenol Aterephthalate) 385 Poly(2-cyanobutyl acrylate) 384 Poly(isobornylmethacrylate) 383 Poly(phenyl methacrylate) 383 Poly(acrylonitrile), PAN383 Poly(Bisphenol C carbonate) 381 Poly(N,N-dimethylacrylamide) 379Poly(butyl cyanoacrylate) 379 Poly(methyl methacrylate), PMMA 378Poly(4-methylstyrene) 377 Poly(4-fluorostyrene) 376 Poly(acrylic acid),PAA 374 Poly(diisobutyl Bisphenol A terephthalate) 373 Poly(dimethylfumarate) 373 Poly(dimethyl itaconate), PDMI 373 Polystyrene, PS 373Poly(3-methylstyrene) 370 Poly(methyl isopropenyl ketone) 370Poly(3,3′-oxydiphenylene carbonate) 364 Poly(1,4-phenylene sulfide), PPS363 Poly(1,4-phenyl ether), PPE 361 Poly(4-methoxy-2-methylstyrene) 361Poly(chlorotrifluoroethylene) 360 Poly(4-isopropylstyrene) 360Poly(isobornyl acrylate) 359 Poly(vinyl chloride), PVC 356Poly(isopropyl methacrylate) 356 Poly(2-chloro-p-xylylene) 356Poly(vinyl alcohol), PVOH, PVA 353 Poly(2-hydroxyethyl methacrylate),PHEMA 350 Poly(2-methoxystyrene) 348 Poly(2,2,2-trifluoroethylmethacrylate) 347 Poly(ethylene terephthalate) 346 Poly(2-hydroxypropylmethacrylate) 345 Poly(2,2,3,3-tetrafluoropropyl methacrylate) 344Poly(vinyl benzoate) 344 Poly(vinyl butyral) 344 Poly(p-xylene) 343Poly(ethyl methacrylate), PEMA 338 Poly[1-(tert-butyl)ethene] 337Poly(4-chlorophenyl vinyl ketone) 336 Poly(glycidyl methacrylate) 334Polylactic acid, PLA 332 Poly(isobutyl methacrylate) 330Poly(2-ethyl-2-methylpropylene terephthalate) 328 Poly(trimethyleneterephthalate) 328 Poly(benzyl methacrylate) 328 Poly(tetrahydrofurfurylmethacrylate) 327 Poly(vinyl fluoride), PVF 326Poly(iminoadipoyliminoheptamethylene), Nylon 7,6 326Poly(iminosebacoyliminodecamethylene), Nylon 10,10 326Poly(4-ethylstyrene) 326 Poly(caprolactam), Nylon 6 324Poly(hexamethylene adipamide), Nylon 6,6 324 Poly(8-aminooctanoic acid),Nylon 8 323 Poly(phenyl vinyl ketone) 323 Poly(hexamethylenesebacamide), Nylon 6,10 320 Poly(4,4′-pentamethylenedibenzoic anhydride)320 Poly(vinyl stearate) 318 Poly(ω-undecanamide), Nylon 11 317Poly(4,4′-tetramethylenedibenzoic anhydride) 316 Poly(norbornene) 316Poly(propyl methacrylate) 316 Poly(octadecyl acrylate) 314Poly(ω-dodecanamide), Nylon 12 313 Poly[(tetramethylene terephthalate)313 Polyglycolide, PGL 312 poly[(prop-1-ene)-alt-(carbon monooxide)] 312Poly(tert-butyl acrylate) 311 Poly(octadecyl methacrylate) 311Poly(1,2-propylene carbonate), PPC 310

In another non-limiting embodiment, suitable fibers include, but are notnecessarily limited to, synthetic fibers, natural fibers, and/ormetallic fibers. Suitable synthetic fibers include, but are notnecessarily limited to, carbon, aramid, poly-para-phenyleneterephthalamide, nylon, rayon, polytetrafluoroethylene (PTFE),polyester, polyacrylonitrile (PAN), the ones mentioned above in Table 1,and the like. Suitable natural fibers include, but are not necessarilylimited to, fibers of animal-based origin, fibers of plant-based origin,and the like. More specifically, suitable animal-based fibers include,but are not necessarily limited to, collagen, keratin, chitin, cashmere,and the like. Suitable plant-based fibers include, but are notnecessarily limited to, hemp, cellulose, bamboo, silk, coir (coconutfiber), abaca (banana fiber), cotton, and the like. One suitablenon-limiting embodiment of poly-para-phenylene terephthalamide isKEVLAR® synthetic fiber available from DuPont, One suitable non-limitingembodiment of polytetrafluoroethylene is TEFLON® synthetic fluoropolymeravailable from Chemours.

In an non-restrictive version, the term metal fibers shall be taken toinclude an element or its oxides, compound, or alloy or combinationthereof that exhibits good thermal conductivity defined as k>5 W/(m-°K), and may, but is not necessarily required to, exhibit good electricalconductivity, defined herein as a resistivity, ρ<10⁻² Ωm. As onenon-limiting example, bronze is an alloy consisting primarily of copperalong with tin and other metals in smaller quantities. Such alloys areencompassed herein in the definition of “metal fibers”. Specificexamples of suitable metal for the metal fibers may include, but are notnecessarily limited to, lithium, sodium, potassium, rubidium, caesium,francium, beryllium, magnesium, calcium, strontium, barium, radium,zinc, molybdenum, cadmium, scandium, titanium, vanadium, chromium,manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium,technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum,tungsten, rhenium, osmium, iridium, platinum, gold, mercury,rutherfordium, dubnium, seaborgium, bohrium, hassium, aluminum, gallium,indium, tin, thallium, lead, bismuth, polonium, lanthanum, cerium,praseodymium, neodymium, promethium, samarium, europium, gadolinium,terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium,actinium, thorium, protactinium, uranium, neptunium, plutonium,americium, curium, berkelium, californium, einsteinium, fermium,mendelevium, nobelium, lawrencium, meitnerium, darmstadtium,roentgenium, copernicium, nihonium, flerovium, moscovium, livermorium,germanium, arsenic, antimony, and combinations thereof. An alternativelist of suitable metal fibers includes, but is not necessarily limitedto, copper, titanium, brass, nickel, chrome, stainless steel, aluminum,as metal elements, as appropriate, and alloys thereof, oxides thereof,compounds thereof, and/or other combinations thereof/

In a different non-limiting embodiment, a “felted” foam may be made byincorporating low melt fibers into the polyurethane foam in addition tothe thermally conductive fibers previously described. Felted foams arecompressed foams that have taken a permanent set due the melted andfused fibers. Low melt fibers are defined as those having a meltingpoint between 50° C. and 200° C. and having a Tg of −50° C. or greater;alternatively a Tg of 37° C. or greater, and in another non-restrictiveversion a Tg of 50° C. or greater. By additionally incorporating lowmelt fibers, foams having surface contouring and improved 3D shaping bymelting low Tg fibers in situ to hold desired conformations while alsogenerating greater strength may be obtained. Such foams would have lowTg zones and high Tg zones to produce both stable and thermoset foams.

In one non-limiting embodiment, the flexible foams herein have aspecific density of greater than 0.5 pounds per cubic foot (pcf)(greater than 8 kg/m³), alternatively from about 0.7 independently toabout 10 pcf (from about 11 to about 160 kg/m³), and in anothernon-restrictive version from about 0.9 independently to about 7 pcf(about 14 to about 112 kg/m³).

In another non-limiting embodiment, the methods and compositions hereincan include methods and compositions made by reaction injection molding(RIM). However, in a different non-restrictive version RIM is excludedfrom the present methods.

In still a different non-limiting embodiment, the flexible foamsdescribed herein may employ conventional blowing agents, includinghalogenated blowing agents. Nevertheless, in a different,non-restrictive version, the flexible foam compositions may have anabsence of halogenated blowing agents.

In a different non-limiting embodiment, the fibers are not continuous,that is, they are chopped, cut, sliced, or otherwise have their lengthreduced. In another non-restrictive version, the flexible foamcompositions only contain one type of fiber, that specified. Thedistribution of the fibers within the flexible foam composition may berandom, homogeneous, and/or uniform. The fibers need not be uniformlyoriented, although they may be. In other words, the fibers need not beoriented in a parallel orientation or any particular orientation,although they may be.

Table 2 shows a non-limiting list of exemplary polyurethane (PU) foamcompositions of the type discussed herein and some PU foams without thefiber reinforcement described in this disclosure. Table 2 also displaysperformance data corresponding to the various foam compositions listedtherein.

TABLE 2 Various PU Foam Compositions (with or without FiberReinforcement) and Performance Factor Results pph Wt % Fiber Fiber Diam.Fiber Length Density 25% IFD Foam Flexible Fiber Fiber in Foam Foam Typemicron micron lb/ft³ lbs 1495 N/A 0.0 0.0 Visco 0.0 0.0 3.68 14.0 1873N/A 0.0 0.0 Visco 0.0 0.0 3.41 9.5 1496 Carbon Fiber C 1.5 1.0 Visco 5.0150 3.67 14.5 1497 Carbon Fiber B 1.5 1.0 Visco 7.0 150 3.71 15.2 1498Carbon Fiber A 1.5 1.0 Visco 7.0 100 3.65 14.1 1499 Carbon Fiber D 1.51.0 Visco 7.0 100 3.65 16.8 1504 Carbon Fiber E 1.5 1.0 Visco 7.0 2503.53 12.2 1505 Carbon Fiber F 1.5 1.0 Visco 7.0 150 3.54 11.5 1506Carbon Fiber G 1.5 1.0 Visco 7.0 200 3.59 9.9 1528 Carbon Fiber A 1.00.6 Visco 7.0 100 3.52 9.9 1529 Carbon Fiber A 2.0 1.3 Visco 7.0 1003.53 10.4 1530 Carbon Fiber A 4.0 2.6 Visco 7.0 100 3.60 12.2 1531Carbon Fiber A 8.0 5.2 Visco 7.0 100 3.63 17.1 1532 Carbon Fiber A 1.00.6 Visco 7.0 100 3.60 9.0 1533 Carbon Fiber A 2.0 1.3 Visco 7.0 1003.76 9.0 1534 Carbon Fiber A 2.0 1.3 Visco 7.0 100 3.57 9.3 1535 CarbonFiber A 1.0 0.6 Visco 7.0 100 3.70 8.5 1874 Carbon Fiber A 5.0 3.2 Visco7.0 100 3.54 13.1 1875 Carbon Fiber A 5.0 3.2 Visco 7.0 100 3.43 9.11965 N/A 0.0 0.0 Conventional 0.0 0.0 1.78 36.5 1966 Carbon Fiber A 1.00.6 Conventional 7.0 100 1.78 36.1 1967 Carbon Fiber A 3.0 1.9Conventional 7.0 100 1.85 39.0 1968 Carbon Fiber A 5.0 3.2 Conventional7.0 100 1.83 39.0 1978 Carbon Fiber A 3.0 1.9 Conventional 7.0 100 1.7542.9 1979 Carbon Fiber A 5.0 3.2 Conventional 7.0 100 1.73 42.4 C940 N/A0.0 0.0 Hybrid 0.0 0.0 1.66 6.8 C941 Carbon Fiber A 5.0 3.2 Hybrid 7.0100 1.62 9.4 18-878 N/A 0.0 0.0 Conventional 0.0 0.0 1.91 41.1 18-660Carbon Fiber A 1.5 1.0 Conventional 7.0 100 1.87 46.0 18-662 N/A 0.0 0.0Conventional 0.0 0.0 1.77 45.3 18-663 Carbon Fiber A 2.3 1.5Conventional 7.0 100 1.48 37.4 18-665 N/A 0.0 0.0 Conventional 0.0 0.01.45 39.4 18-909 N/A 0.0 0.0 Conventional 0.0 0.0 1.94 38.9 18-403 N/A0.0 0.0 Visco 0.0 0.0 3.12 14.1 18-404 N/A 0.0 0.0 Visco 0.0 0.0 3.0111.5 T721 N/A 0.0 0.0 Visco 0.0 0.0 2.37 8.2 T722 Carbon Fiber A 1.0 0.6Visco 7.0 100 2.68 8.8 T723 Carbon Fiber A 1.5 1.0 Visco 7.0 100 2.668.8 T793 N/A 0.0 0.0 Visco 0.0 0.0 2.64 10.0 T794 Carbon Fiber A 1.0 0.6Visco 7.0 100 2.51 8.5 T795 Carbon Fiber A 1.5 1.0 Visco 7.0 100 2.508.5 18-359 Carbon Fiber A 1.5 1.0 Visco 0.0 0.0 2.85 8.7 L2405 N/A 0.00.0 Conventional 0.0 0.0 1.49 17.6 L2420 Carbon Fiber A 0.5 0.3Conventional 7.0 100 1.46 17.0 L2406 Carbon Fiber A 1.0 0.6 Conventional7.0 100 1.51 16.9 L2421 Carbon Fiber A 1.5 1.0 Conventional 7.0 100 1.4516.9 L2407 Carbon Fiber A 2.0 1.3 Conventional 7.0 100 1.51 19.0 L2408Carbon Fiber A 3.0 1.9 Conventional 7.0 100 1.56 20.3 L2409 Carbon FiberA 5.0 3.2 Conventional 7.0 100 1.54 22.0 L2375 N/A 0.0 0.0 Conventional0.0 0.0 1.78 22.7 L2422 Carbon Fiber A 0.5 0.3 Conventional 7.0 100 1.8722.2 L2376 Carbon Fiber A 1.0 0.6 Conventional 7.0 100 1.79 23.0 L2423Carbon Fiber A 1.5 1.0 Conventional 7.0 100 1.74 23.2 L2377 Carbon FiberA 2.0 1.3 Conventional 7.0 100 1.77 23.3 L2378 Carbon Fiber A 3.0 1.9Conventional 7.0 100 1.82 25.0 L2379 Carbon Fiber A 5.0 3.2 Conventional7.0 100 1.85 28.2 L2415 N/A 0.0 0.0 Conventional 0.0 0.0 1.96 25.7 L2424Carbon Fiber A 0.5 0.3 Conventional 7.0 100 2.01 30.7 L2416 Carbon FiberA 1.0 0.6 Conventional 7.0 100 3.00 33.3 L2425 Carbon Fiber A 1.5 1.0Conventional 7.0 100 2.03 29.3 L2417 Carbon Fiber A 2.0 1.3 Conventional7.0 100 2.02 38.0 L2418 Carbon Fiber A 3.0 1.9 Conventional 7.0 100 2.0532.3 L2419 Carbon Fiber A 5.0 3.2 Conventional 7.0 100 2.00 41.8 L2410N/A 0.0 0.0 Conventional 0.0 0.0 2.66 18.3 L2426 Carbon Fiber A 0.5 0.3Conventional 7.0 100 2.56 18.3 L2411 Carbon Fiber A 1.0 0.6 Conventional7.0 100 2.58 19.8 L2427 Carbon Fiber A 1.5 1.0 Conventional 7.0 100 2.4323.4 L2412 Carbon Fiber A 2.0 1.3 Conventional 7.0 100 2.59 21.5 L2413Carbon Fiber A 3.0 1.9 Conventional 7.0 100 2.74 21.0 L2414 Carbon FiberA 5.0 3.2 Conventional 7.0 100 2.67 26.0 L2538 N/A 0.0 0.0 Visco 0.0 0.03.09 9.2 L2540 Nickel Fiber 5.0 3.2 Visco 8.0 200 3.15 10.7 L2541 NickelFiber 5.0 3.2 Visco 2.0 200 3.13 9.5 L2542 Copper Fiber 5.0 3.2 Visco8.0 200 3.14 9.4 L2584 Chitosan Fiber 5.0 3.2 Visco 0.0 0.0 3.09 8.9L2586 Nickel Fiber 1.0 0.6 Visco 8.0 200 3.05 9.0 L2587 Nickel Fiber 1.00.6 Visco 2.0 200 3.02 8.3 L2588 Copper Fiber 1.0 0.6 Visco 8.0 200 3.188.7 L2589 Chitosan Fiber 1.0 0.6 Visco 0.0 0.0 3.30 13.1

To improve adhesion between the fiber and the flexible foam structure,in another non-limiting embodiment, the fibers may be surface treated.The surface treatment may be selected from the group consisting of dryoxidation in the presence of a gas selected from the group consisting ofair, oxygen, CO₂, and combinations thereof; plasma etching; wetoxidation; deposition of an active form of carbon; wiskerization; plasmapolymerization; grafting of polymers onto the fiber surface; sizing ofthe fibers with a material selected from the group consisting of epoxy,urethane, polyester, organic adhesives, gels, and combinations thereof;and combinations thereof. More particularly, suitable gels include, butare not necessarily limited to, hydrogels, gelatins, thermoplastictriblock and/or diblock gels as referenced in Peterson ChemicalTechnology LLC's U.S. Pat. No. 8,933,139 B1 incorporated herein byreference in its entirety, and the like. In one non-limiting embodiment,the surface treatment has an absence of silanes.

It will be appreciated that the polyols, polyisocyanates, and gelationcatalysts can be those conventionally used for polyurethane flexiblefoams. Similarly, the components of the other flexible foam compositionsmentioned herein may also be conventional. The flexible foamcompositions may also contain useful amounts of conventionally employedadditives such as stabilizers, antioxidants, antistatic agents,antimicrobial agents, ultraviolet stabilizers, phase change materials,surface tension modifiers such as silicone surfactants, emulsifyingagents, and/or other surfactants, extender oils, solid flame retardants,liquid flame retardants, grafting polyols, compatiblehydroxyl-containing chemicals which are completely saturated orunsaturated in one or more sites, solid or liquid fillers, antiblockingagents, colorants such as inorganic pigments or colorants, carbon black,organic colorants or dyes, reactive organic colorants or dyes,heat-responsive colorant, heat-responsive pigment, heat-responsive dye,pH-responsive colorant, pH-responsive pigment, pH-responsive dye andcombinations thereof, fragrances, and thermally-conductive materialswith thermal conductivity values in the range of 0.1 W/(m-° K) to 2000W/(m-° K) such as talc, melamine, carbon black, graphite, aluminumoxide, aluminum nitride, zinc oxide, ferric oxide, diamond, titaniumdioxide, magnesium oxide, magnesium silicate, silicon carbide, boronnitride, sodium carbonate, sodium bicarbonate, calcium carbonate, bariumsulfate, metal flakes such as aluminum powder, and viscosity-modifierssuch as fumed silica and clays, and other polymers in minor amounts andthe like to an extent not affecting or substantially decreasing thedesired properties of polyurethane foam herein.

The fiber reinforced flexible foam compositions and structures disclosedherein may be employed in many types of flexible foams including, butnot limited to, open cell or closed cell; flexible polyurethane foam;polyether polyurethane foam; high-resiliency (HR) polyether polyurethanefoam; flexible viscoelastic foam; flexible resilient polyurethane foam;flexible high resilient (HR) foam; viscoelastic polyether polyurethanefoam; polyester polyurethane foam; latex foam; foamed polyethyleneincluding low-density polyethylene (LDPE) foam, first grade ofpolyethylene (PE); foamed polypropylene including expanded polypropylene(EPP) and polypropylene paper (PPP); polystyrene (PS) foam, includingexpanded polystyrene (EPS), extruded polystyrene foam (XPS) andpolystyrene paper (PSP); foamed silicone, melamine foam, ethylene-vinyl(EVA) foam, the copolymers of ethylene and vinyl acetate; also referredto as polyethylene-vinyl acetate (PEVA); nitrile rubber (NBR) foam, thecopolymers of acrylonitrile (ACN) and butadiene; polychloroprene foam,also known as Neoprene; polyimide foam; and combinations thereof.

The foam compositions and foam structures disclosed herein may be usedin the manufacture of a variety of articles such as, without limitation,rebond carpet pads, floor mats, bath mats, pet beds, shoe inserts,medical foams, mattresses, pillows, bedding products, seat cushions,seat backs, head rests, armrests and combinations thereof.

As discussed above, it has been discovered that flexible foamcompositions disclosed herein may exhibit improved properties forperformance.

FIGS. 1 and 2 are microphotographs of a plurality of fiber-reinforcedstruts in different non-limiting embodiments of polyurethane foamcompositions as described herein. Close examination will reveal that thepolyurethane foam structures have conventional struts and that aplurality of carbon fibers is aligned with the struts, positioned on orwithin the struts. FIG. 1 is a microphotograph of a polyurethane foammade demonstrating mixing carbon fibers into the polyol side first,whereas FIG. 2 is a microphotograph of a polyurethane foam madedemonstrating mixing carbon fibers by way of a concentrated slurry. InFIG. 1, some of the many fibers visible are pointed out by a few whitearrows. In FIG. 2, some of the many fibers visible are pointed out by afew black arrows. In each microphotograph, many more fibers associatedwith struts are visible than are pointed out.

As shown in FIGS. 3-5, polyurethane foam compositions that were made andtested that contained fibers displayed better IFD and compression lossesthan the polyurethane foam compositions that did not contain fibers. TheIFD data were developed according to ASTM D3574 Test B1.

More specifically, FIG. 3 is a graph illustrating the IFD value ofexemplary carbon-fiber reinforced polyurethane foams as a function ofthe amount of carbon fiber loaded into the polyol that is reacted tomake the polyurethane foam. It is readily seen that the IFD increaseswith carbon fiber loading.

FIG. 4 is a bar graph illustrating that including flexible fiber reducesfatigue losses as measured by IFD for nickel fiber, copper fiber andchitosan fiber at two different usage levels reduces fatigue loss in allcases. FIG. 5 is a graph illustrating that flexible fiber reducescompression losses as measured by height loss for three different trialswith different fiber loadings into the polyol that is reacted to makethe polyurethane foam. Generally, as the amount of fiber levelincreases, the height loss is reduced.

Based on the data generated from the testing of exemplary embodiments ofthe flexible foam compositions described herein, the inclusion offibers, e.g. thermally conductive fibers such as carbon fibers, appearsto have an effect at increasing the IFD of and improving the compressionlosses of the foams, making the overall foams more rigid and thusfirmer. In addition, the heat transfer effect seems to accelerate as thedensity of the carbon fiber in the foam increases. Finally, it appearsthat a strut reinforcement mechanism that may be created by the use ofcarbon fibers in the foam compositions may result in increased rigidityof the individual struts. This increases a foam's propensity to returnto its original state after deformation and thus potentially improvingcompression set performance.

Many modifications may be made in the methods of and implementation ofthis invention without departing from the spirit and scope thereof thatare defined only in the appended claims. For example, the exactfoam-forming components, e.g. polyols, polyisocyanates, carbon fibers,gelation catalysts, polymer fibers and other additives, the proportionsof these components used to make or treat the foams discussed hereinused may be different from those used explicitly mentioned or suggestedhere. Additionally, techniques and methods for improving the propertiesand/or processing characteristics of polyurethane foam compositions andstructures other than those specifically mentioned may find utility inthe methods herein.

The words “comprising” and “comprises” as used throughout the claims isinterpreted “including but not limited to”.

The present invention may suitably comprise, consist or consistessentially of the elements disclosed and may be practiced in theabsence of an element not disclosed. For instance, a flexible foamcomposition is provided that may consist of or consist essentially of: aflexible foam structure, where the flexible foam structure comprises,consists of, or consists essentially of a plurality of struts and aplurality of fibers, where the fibers are associated with the struts,and optionally where the fibers are selected from the group consistingof carbon fibers, polymer fibers having a glass transition temperature(Tg) of −50° C. (−58° F.) or greater, and combinations thereof.

In another non-limiting embodiment, there may be provided a flexiblefoam composition comprising, consisting essentially of, or consisting ofa flexible foam structure, where the flexible foam structure comprises,consists of, or consists essentially of a plurality of struts and aplurality of thermally conductive carbon fibers, where a majority of thethermally conductive carbon fibers are associated with the struts andare substantially parallel to their respective associated strut, wherethe thermally conductive fiber loading is an amount effective to improvea property selected from the group consisting of increase static thermalconductivity, greater indentation force deflection (IFD), and/orimproved height retention or durability, as compared with an otherwiseidentical flexible foam composition absent the thermally conductivecarbon fibers. In a non-limiting embodiment as used herein, heightretention is a measurement of dynamic fatigue.

As used herein, the terms “comprising,” “including,” “containing,”“characterized by,” and grammatical equivalents thereof are inclusive oropen-ended terms that do not exclude additional, unrecited elements ormethod acts, but also include the more restrictive terms “consisting of”and “consisting essentially of” and grammatical equivalents thereof. Asused herein, the term “may” with respect to a material, structure,feature or method act indicates that such is contemplated for use inimplementation of an embodiment of the disclosure and such term is usedin preference to the more restrictive term “is” so as to avoid anyimplication that other, compatible materials, structures, features andmethods usable in combination therewith should or must be, excluded.

As used herein, the singular forms “a,” “an,” and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise.

As used herein, the term “and/or” includes any and all combinations ofone or more of the associated listed items.

As used herein, the term “about” in reference to a given parameter isinclusive of the stated value and has the meaning dictated by thecontext (e.g., it includes the degree of error associated withmeasurement of the given parameter.

What is claimed is:
 1. A flexible foam composition comprising: aflexible foam structure, where the flexible foam structure comprises aplurality of struts; and a plurality of fibers, where a majority of thefibers are associated with the struts.
 2. The flexible foam compositionof claim 1 where: the fibers have a diameter between about 0.1 to about25 microns; and the fibers have a length between about 30 to about 490microns.
 3. The flexible foam composition of claim 2 where the fibershave a length between about 90 and about 160 microns.
 4. The flexiblefoam composition of claim 1 where the fibers are thermally conductivefibers, and the thermally conductive fiber loading is an amounteffective to increase the static thermal conductivity as compared withan otherwise identical flexible foam composition absent the fibers. 5.The flexible foam composition of claim 1 where the flexible foamstructure comprises a polyurethane foam and fiber loading based on theamount of polyol ranges from about 0.01 to about 50 pph.
 6. The flexiblefoam composition of claim 1 where fiber loading ranges from about 0.01to about 30 percent by weight in the flexible foam composition.
 7. Theflexible foam composition of claim 1 where the composition has a greaterindentation force deflection (IFD) as compared with an otherwiseidentical flexible foam composition absent the fibers.
 8. The flexiblefoam composition of claim 1 where the composition has an improvedproperty as compared with an otherwise identical flexible foamcomposition absent the fibers, where the improved property is selectedfrom the group consisting of: compression set, indentation forcedeflection (IFD), height retention, thermal conductivity, andcombinations thereof.
 9. The flexible foam composition of claim 1 wherethe fibers have been surface treated to improve adhesion between thefibers and the flexible foam structure, where the surface treatment isselected from the group consisting of: dry oxidation in the presence ofa gas selected from the group consisting of air, oxygen, CO₂, andcombinations thereof; plasma etching; wet oxidation; deposition of anactive form of carbon, wiskerization, plasma polymerization, grafting ofpolymers onto the fiber surface, sizing of the fibers with a materialselected from the group consisting of epoxy, urethane, polyester,organic adhesives, gels, and combinations thereof; and combinationsthereof.
 10. The flexible foam composition of claim 1 where the fibersare selected from the group consisting of: synthetic fibers selectedfrom the group consisting of carbon, aramid, poly-para-phenyleneterephthalamide, nylon, rayon, polytetrafluoroethylene (PTFE),polyester, and polyacrylonitrile (PAN); fibers of animal-based origin;fibers of plant-based origin; metal fibers selected from the groupconsisting of metal elements, oxides thereof, compounds thereof, alloysthereof, and combinations thereof; and combinations of these.
 11. Theflexible foam composition of claim 10 where: the fibers of animal-basedorigin are selected from the group consisting of collagen, keratin,chitin, silk, and combinations thereof; and the fibers of plant-basedorigin are selected from the group consisting of hemp, cellulose,bamboo, coir (coconut fiber), abaca (banana fiber), and cotton.
 12. Theflexible foam composition of claim 1 where the fibers are selected fromthe group consisting of homopolymer and/or copolymer fibers having aglass transition temperature (Tg) of −50° C. (−58° F.) or greater,carbon fibers, and combinations thereof.
 13. The flexible foamcomposition of claim 1 additionally comprising a plurality of low meltfibers having a melting point between 50° C. and 200° C. and having a Tgof −50° C. or greater and where the flexible foam composition is afelted foam.
 14. The flexible foam composition of claim 1 where thefibers are carbon fibers.
 15. The flexible foam composition of claim 1where a majority of the fibers are substantially parallel to theirrespective associated strut.
 16. The flexible foam composition of claim1 where the fibers are thermally conductive fibers having a thermalconductivity of at least 1 W/m-K.
 17. An article of manufacturecomprising the composition of claim 1 where the flexible foam structureis selected from the group consisting of: flexible polyurethane foam,polyether polyurethane foam, high-resiliency (HR) polyether polyurethanefoam, flexible viscoelastic foam, flexible resilient polyurethane foam,flexible high resilient (HR) foam, viscoelastic polyether polyurethanefoam, polyester polyurethane foam, latex foam, foamed polyethylene,foamed polypropylene, polystyrene (PS) foam, foamed silicone, melaminefoam, ethylene-vinyl (EVA) foam, nitrile rubber (NBR) foam, polyimidefoam, and combinations thereof.
 18. An article of manufacture comprisingthe flexible foam composition of claim 1 where the article is selectedfrom the group consisting of rebond carpet pads, floor mats, bath mats,pet beds, shoe inserts, medical foams, mattresses, pillows, beddingproducts, seat cushions, seat backs, head rests, armrests andcombinations thereof.
 19. A flexible foam composition comprising: aflexible foam structure, where the flexible foam structure comprises aplurality of struts; and a plurality of fibers, where a majority of thefibers are associated with the struts, where the fibers are selectedfrom the group consisting of carbon fibers, homopolymer and/or copolymerfibers having a glass transition temperature (Tg) of −50° C. (−58° F.)or greater, and combinations thereof; where: the fibers have a diameterbetween about 0.1 to about 25 microns; the fibers have a length betweenabout 30 to about 490 microns; and fiber loading where the flexible foamstructure is polyurethane foam is based on the amount of polyol rangesfrom about 0.01 to about 50 pph; and fiber loading where the flexiblefoam is other than polyurethane foam ranges from about 0.01 to 30percent by weight in the final flexible foam.
 20. The flexible foamcomposition of claim 19 where the fibers are thermally conductive fibershaving a thermal conductivity of at least 1 W/m-K and the fiber loadingis an amount effective to increase the static thermal conductivity ascompared with an otherwise identical flexible foam absent the fibers.21. The flexible foam composition of claim 19 where a foam property isimproved as compared with an otherwise identical flexible foamcomposition absent the fibers, where the improved property is selectedfrom the group consisting of: indentation force deflection (IFD);compression set; height retention; and combinations thereof.
 22. Theflexible foam composition of claim 19 where the thermally conductivefibers have been surface treated to improve adhesion between thethermally conductive fiber and the flexible foam structure, where thesurface treatment is selected from the group consisting of: dryoxidation in the presence of a gas selected from the group consisting ofair, oxygen, CO₂, and combinations thereof; plasma etching; wetoxidation; deposition of an active form of carbon, wiskerization, plasmapolymerization, grafting of polymers onto the thermally conductive fibersurface, sizing of the thermally conductive fibers with a materialselected from the group consisting of epoxy, urethane, polyester,organic adhesives, gels, and combinations thereof; and combinationsthereof.
 23. The flexible foam composition of claim 19 where thethermally conductive fibers are carbon fibers.
 24. An article ofmanufacture comprising the composition of claim 19 where the flexiblefoam structure is selected from the group consisting of: flexiblepolyurethane foam, polyether polyurethane foam, high-resiliency (HR)polyether polyurethane foam, flexible viscoelastic foam, flexibleresilient polyurethane foam, flexible high resilient (HR) foam,viscoelastic polyether polyurethane foam, polyester polyurethane foam,latex foam, foamed polyethylene, foamed polypropylene, polystyrene (PS)foam, foamed silicone, melamine foam, ethylene-vinyl (EVA) foam, nitrilerubber (NBR) foam, polyimide foam, and combinations thereof.
 25. Aflexible foam composition comprising: a flexible foam structure, wherethe polyurethane foam structure comprises a plurality of struts; and aplurality of carbon fibers, where a majority of the carbon fibers areassociated with the struts and are substantially parallel to theirrespective associated strut; and where fiber loading is an amounteffective to improve a foam property selected from the group consistingof: the composition has a greater indentation force deflection (IFD) ascompared with an otherwise identical flexible foam composition absentthe carbon fibers; the composition has a greater static thermalconductivity as compared with an otherwise identical flexible foamcomposition absent the carbon fibers; the composition has an improvedcompression set as compared with an otherwise identical flexible foamcomposition absent the carbon fibers; the composition has improvedheight retention as compared with an otherwise identical flexible foamcomposition absent the carbon fibers; the composition has improvedthermal conductivity as compared with an otherwise identical flexiblefoam composition absent the carbon fibers; and combinations thereof. 26.The flexible foam composition of claim 25 where: the thermallyconductive carbon fibers have a diameter between about 0.1 to about 25microns; and the thermally conductive carbon fibers have a lengthbetween about 30 to about 490 microns.
 27. The flexible foam compositionof claim 25 where thermally conductive carbon fiber loading based on theamount of polyol ranges from about 0.01 to about 50 pph.
 28. Theflexible foam composition of claim 25 where fiber loading ranges fromabout 0.01 to about 30 percent by weight in the flexible foamcomposition.
 29. The flexible foam composition of claim 25 where thethermally conductive carbon fibers have been surface treated to improveadhesion between the thermally conductive carbon fiber and the flexiblefoam structure, where the surface treatment is selected from the groupconsisting of: dry oxidation in the presence of a gas selected from thegroup consisting of air, oxygen, CO₂, and combinations thereof; plasmaetching; wet oxidation; deposition of an active form of carbon,wiskerization, plasma polymerization, grafting of polymers onto thethermally conductive fiber surface, sizing of the thermally conductivefibers with a material selected from the group consisting of epoxy,urethane, polyester, organic adhesives, gels, and combinations thereof;and combinations thereof.